CN112119115A - Powdery liquid crystalline resin for hot press molded article and hot press molded article - Google Patents
Powdery liquid crystalline resin for hot press molded article and hot press molded article Download PDFInfo
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- CN112119115A CN112119115A CN201980032739.1A CN201980032739A CN112119115A CN 112119115 A CN112119115 A CN 112119115A CN 201980032739 A CN201980032739 A CN 201980032739A CN 112119115 A CN112119115 A CN 112119115A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/34—Feeding the material to the mould or the compression means
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- Polyesters Or Polycarbonates (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
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- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
[ problem ] to provide: a powdery liquid crystalline resin capable of producing a hot press molded article having a small anisotropy and a hot press molded article using the same. [ solution ] the problem is solved by forming the following powdery liquid crystalline resin for hot press molded articles: the liquid crystalline resin contains 90 mol% or more of structural units derived from an aromatic hydroxycarboxylic acid in the entire structural units, and has an average particle diameter of 10to 300 [ mu ] m. The crystallinity is preferably 10% or more and 60% or less. The difference Δ Tm between the melting points Tm2 and Tm1 (Tm2-Tm1 starting temperature) as measured by a differential scanning calorimeter is preferably 30 ℃ to 90 ℃.
Description
Technical Field
The present invention relates to a powdery liquid crystalline resin for hot press molded articles and a hot press molded article.
Background
Liquid crystalline resins represented by liquid crystalline polyester resins are widely used in various fields because of their excellent properties such as high flowability, low burr property, and reflow resistance. However, since the liquid crystalline resin has a property of being oriented in the resin flow direction during cooling of molding (orientation), the resulting molded article may have anisotropy having different physical properties in the resin flow direction and in the direction perpendicular thereto.
The hot press molding is a molding method in which resin powder is hot press molded at a temperature at which the resin melts, and the orientation of the liquid crystalline resin can be suppressed to a small extent as compared with injection molding in which the resin is melted at a high temperature at which the resin flows, but the anisotropy of the obtained molded product is not yet eliminated. Patent document 1 describes a method for producing a liquid crystal resin sheet, in which a plurality of liquid crystal resins having different heat distortion temperatures are pulverized and mixed to prepare a molding material, and the molding material is pressure-molded in a predetermined temperature range.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2008-30397
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing: a powdery liquid crystalline resin capable of producing a hot press molded article having a small anisotropy and a hot press molded article using the same.
Means for solving the problems
The present invention relates to the following.
[1] A powdery liquid crystalline resin for hot press moldings, which contains 90 mol% or more of a structural unit derived from an aromatic hydroxycarboxylic acid in all the structural units, and which has an average particle diameter of 10to 300 [ mu ] m.
[2] The powdery liquid crystalline resin according to [1], which has a crystallinity of 10% or more and 60% or less.
[3] The powdery liquid crystalline resin according to [1] or [2], wherein a difference Δ Tm (Tm2-Tm1 onset temperature) between the melting point Tm2 and the melting point Tm1 as measured by a differential scanning calorimeter is 30 ℃ or more and 90 ℃ or less.
[4] The powdery liquid crystalline resin according to any one of [1] to [3], wherein a melting point Tm2 measured by a differential scanning calorimeter is 250 ℃ or more and 400 ℃ or less.
[5]According to [1]～[4]The powdery liquid crystalline resin according to any one of the above items, wherein the resin composition has a cylinder temperature and a shear rate of 100sec which are 10to 30 ℃ higher than a melting point Tm2 measured by a differential scanning calorimeter-1The melt viscosity measured below is 10 pas or more and 1000 pas or less.
[6] The powdery liquid crystalline resin according to any one of [1] to [5], wherein the ratio of the maximum particle diameter to the average particle diameter (maximum particle diameter/average particle diameter) is 5 or less.
[7] A powder material for hot press molded articles, which comprises the powdery liquid crystalline resin according to any one of [1] to [6 ].
[8] A hot press molded article comprising the powdery liquid crystalline resin according to any one of [1] to [6 ].
[9] The hot press molded article according to item [8], which is in the form of a film having a thickness of less than 2 mm.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a powdery liquid crystalline resin capable of producing a hot press molded article having a small anisotropy and a hot press molded article using the same.
Drawings
Fig. 1 is an optical micrograph of the surface of the hot press molded film obtained in example 1.
Fig. 2 is an optical micrograph of the surface of the hot press molded film obtained in comparative example 1.
Detailed Description
Hereinafter, an embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within a range not to impair the effects of the present invention.
[ powdery liquid crystalline resin ]
The powdery liquid crystalline resin for hot press molded articles of the present embodiment (hereinafter, also simply referred to as "powdery liquid crystalline resin") contains 90 mol% or more of a structural unit derived from an aromatic hydroxycarboxylic acid in all the structural units. In the present specification, the term "powder" refers to a composition comprising fine particles having an average particle diameter of about 0.1 to 1000 μm, and the term "average particle diameter" refers to an arithmetic average particle diameter based on a volume basis in a laser diffraction/scattering particle size distribution measurement method. The average particle diameter can be measured, for example, using a laser diffraction/scattering particle size distribution measuring device LA-920 manufactured by horiba, Ltd.
"liquid-crystalline" means having a property of forming an optically anisotropic melt phase. The properties of the anisotropic molten phase can be confirmed by a conventional polarized light inspection method using a crossed polarizing plate. More specifically, the confirmation of the anisotropic melt phase can be carried out as follows: the molten sample placed on the Leitz hot stage was observed at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarizing microscope. The resin having liquid crystallinity is as follows: when inspection is performed between crossed polarizers, polarized light is generally transmitted even in a molten stationary state, and anisotropy is optically exhibited.
The liquid crystalline resin preferably contains at least 1 selected from the group consisting of a liquid crystalline polyester and a liquid crystalline polyesteramide containing a structural unit derived from an aromatic hydroxycarboxylic acid. The liquid crystalline polyester and the liquid crystalline polyester amide are not particularly limited, but preferably an aromatic polyester or an aromatic polyester amide, and more preferably contain at least one resin selected from the group consisting of a wholly aromatic polyester and a wholly aromatic polyester amide. In addition, a polyester partially containing an aromatic polyester or an aromatic polyester amide in the same molecular chain may also be used.
More specifically, the aromatic polyester or aromatic polyester amide containing a structural unit derived from an aromatic hydroxycarboxylic acid includes:
(1) a polyester mainly comprising 1 or 2 or more species selected from structural units derived from an aromatic hydroxycarboxylic acid and a derivative thereof;
(2) a polyester mainly comprising (a) 1 or 2 or more species selected from structural units derived from an aromatic hydroxycarboxylic acid and a derivative thereof, and (b) 1 or 2 or more species selected from structural units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof;
(3) a polyester mainly comprising (a) 1 or 2 or more species selected from structural units derived from an aromatic hydroxycarboxylic acid and a derivative thereof, (b) 1 or 2 or more species selected from structural units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and a derivative thereof, and (c) 1 or 2 or more species selected from structural units derived from an aromatic diol, an alicyclic diol, an aliphatic diol, and a derivative thereof;
(4) a polyesteramide mainly comprising (a) 1 or 2 or more species selected from structural units derived from aromatic hydroxycarboxylic acids and derivatives thereof, (b) 1 or 2 or more species selected from structural units derived from aromatic hydroxyamines, aromatic diamines, and derivatives thereof, and (c) 1 or 2 or more species selected from structural units derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof;
(5) mainly comprising (a) 1 or 2 or more species selected from structural units derived from aromatic hydroxycarboxylic acids and derivatives thereof, (b) 1 or 2 or more species selected from structural units derived from aromatic hydroxyamines, aromatic diamines, and derivatives thereof, (c) 1 or 2 or more species selected from structural units derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof, and (d) 1 or 2 or more species selected from structural units derived from aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof. Further, the above-mentioned components may be combined with a molecular weight modifier as necessary.
Examples of the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid (HBA), 3-hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid (HNA), 5-hydroxy-1-naphthoic acid, 4 '-hydroxy [1,1' -biphenyl ] -4-carboxylic acid, and derivatives thereof. Examples of the derivative include compounds obtained by substituting an aromatic ring (aromatic ring) of the aromatic hydroxycarboxylic acid with a substituent having 0to 20 carbon atoms (preferably 0to 10 carbon atoms). Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, a halogen atom, a hydroxyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, a mercapto group, an alkylthio group, an alkenylthio group, an arylthio group, an aralkylthio group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an amino group, a mono-or dialkylamino group, a mono-or diphenylamino group, an acylamino group, an epoxy group-containing group, an acyl group, an oxy group, and an isocyanate group. The liquid crystalline resin may have 1 or 2 or more of these structural units derived from the aromatic hydroxycarboxylic acid.
Examples of the other monomers constituting the liquid crystalline resin include aromatic diols such as 2, 6-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 4' -dihydroxybiphenyl, hydroquinone, resorcinol, a compound represented by the following general formula (I) and a compound represented by the following general formula (II); aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4' -diphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III); aromatic amines such as p-aminophenol and p-phenylenediamine.
(X: is selected from the group consisting of alkylene (C)1～C4) Alkylidene, -O-, -SO2Radicals in the group-S-and-CO-And (4) clustering. )
(Y is selected from the group consisting of- (CH)2)n- (n-1-4) and-O (CH)2)nAnd O- (n is 1 to 4). )
The liquid crystalline resin contains 90 mol% or more of a structural unit derived from an aromatic hydroxycarboxylic acid in the entire structural unit. The structural unit derived from an aromatic hydroxycarboxylic acid is preferably 93 mol% or more, more preferably 95 mol% or more. The upper limit value is not particularly limited, and may be, for example, 98 mol% or less. By using a powdery liquid crystalline resin (liquid crystalline resin fine particles) containing 90 mol% or more of a structural unit derived from an aromatic hydroxycarboxylic acid, the orientation of the resin during hot press molding is small, and therefore, a hot press molded article having small anisotropy can be produced.
The content of the structural unit derived from the aromatic hydroxycarboxylic acid in the liquid crystalline resin can be measured by thermal decomposition gas chromatography or the like.
The method for producing the liquid crystalline polyester and the liquid crystalline polyester amide is not particularly limited, and the liquid crystalline polyester amide can be produced by a known method using the above monomer compound (or the mixture of monomers) by a direct polymerization method or an ester exchange method, and usually a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, or the like, or a combination of 2 or more of them can be used, and preferably a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is used. In the case of a compound having an ester-forming ability, the compound may be used as it is for polymerization, or a derivative having an ester-forming ability may be used which is modified from a precursor by an acylating agent or the like at a stage prior to polymerization. Examples of the acylating agent include carboxylic acid anhydrides such as acetic anhydride.
In the polymerization, various catalysts can be used. Typical examples of the catalyst that can be used include metal salt catalysts such as potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, tris (2, 4-pentanedionato) cobalt (III), and organic compound catalysts such as N-methylimidazole and 4-dimethylaminopyridine. The amount of the catalyst used is usually about 0.001 to 1% by mass, particularly preferably about 0.01 to 0.2% by mass, based on the total weight of the monomers.
The deflection temperature under load of the liquid crystalline resin measured according to ASTM D648 is preferably 150 ℃ or more and 280 ℃ or less, more preferably 160 ℃ or more and 270 ℃ or less, and further preferably 170 ℃ or more and 260 ℃ or less. By setting the deflection temperature under load to 150 ℃ or higher and 280 ℃ or lower, the orientation of the resin during hot press molding can be further reduced, and a hot press molded article having less anisotropy can be produced.
In the liquid crystalline resin, various fibrous, powdery, and plate-like inorganic and organic fillers may be blended in the production stage. Examples of the fibrous filler include inorganic fibrous materials such as glass fibers, ground glass fibers, carbon fibers, asbestos fibers, silica/alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, and fibers of silicates such as wollastonite, magnesium sulfate fibers, aluminum borate fibers, and metallic fibrous materials such as stainless steel, aluminum, titanium, copper, and brass. A typical fibrous filler is glass fiber. High-melting organic fibrous materials such as polyamide, fluororesin, polyester resin, and acrylic resin may also be used.
Examples of the particulate filler include carbon black, graphite, silica, quartz powder, glass beads, glass spheres, glass powder, silicates such as calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, and wollastonite, oxides of metals such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, and alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, and ferrite, silicon carbide, silicon nitride, boron nitride, and various metal powders.
Examples of the plate-like filler include mica, glass flakes, talc, and various metal foils.
These inorganic and organic fillers may be used singly or in combination of two or more.
The content of the filler may be 0to 100 parts by mass with respect to 100 parts by mass of the liquid crystalline resin.
The liquid crystalline resin may contain additives such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, pigments, and crystal nucleating agents as other components.
The powdery liquid crystalline resin has an average particle diameter of 10to 300 μm, preferably 10to 100 μm, and more preferably 10to 50 μm. By setting the average particle diameter to 10m or more and 300 μm or less, the orientation of the resin during hot press molding can be reduced, and a hot press molded article having low anisotropy can be produced. The above is the case for the "average particle diameter".
The ratio of the maximum particle diameter to the average particle diameter (maximum particle diameter/average particle diameter) of the powdery liquid crystalline resin is preferably 5 or less, more preferably 2.5 or less. The lower limit is not particularly limited, and may be 1 or more. The "maximum particle diameter" refers to the maximum value among values measured by a laser diffraction/scattering particle size distribution measurement method. By setting the ratio of the maximum particle diameter to the average particle diameter (maximum particle diameter/average particle diameter) to 5 or less, the powder flowability at the time of hot press molding can be improved.
The liquid crystalline resin powder having the average particle diameter may be produced by using the liquid crystalline resin obtained by the liquid crystalline resin production method as it is, or by using the liquid crystalline resin obtained by the following method: the liquid crystalline resin obtained by the above-mentioned method for producing a liquid crystalline resin is molded into pellets, fibers, films, etc., and the obtained material is subjected to pulverization treatment by dry pulverization, wet pulverization, or freeze pulverization using a jet mill, a bead mill, a hammer mill, a ball mill, a chopper mill, a stone mill, etc. In addition, it is also possible to use: a method of dissolving a liquid crystalline resin in a solvent and then spray-drying the solution, a method of precipitating a poor solvent by contacting the solution with a poor solvent after forming an emulsion in a solvent, a method of drying the solution by drying an organic solvent after forming an emulsion in a solvent, and the like. The following method may also be used: the liquid crystalline resin and the non-liquid crystalline resin are mixed and then the non-liquid crystalline resin is dissolved and removed with a solvent to obtain a powdery liquid crystalline resin having the above average particle diameter. In addition, the following method may be used: the oligomer of the liquid crystalline resin is pulverized and then subjected to solid-phase polymerization to obtain a powdery liquid crystalline resin having the above average particle diameter.
Among these, it is preferable that the fine particles are made into a powder having the above average particle diameter in an environment of 30 to 50 ℃ lower than the glass transition temperature Tg of the liquid crystalline resin constituting the powdery liquid crystalline resin. For example, a powder micronized under an environment of-40 ℃ higher than the glass transition temperature Tg of the liquid crystalline resin (under an environment 40 ℃ lower than Tg) can be used. The powder micronized in an environment 30 to 50 ℃ lower than the glass transition temperature Tg of the liquid crystalline resin generally has a narrow particle size distribution, excellent powder flowability, and low crystallinity.
The crystallinity of the powdery liquid crystalline resin is 10% or more and 60% or less, preferably 12% or more and 58% or less, and more preferably 15% or more and 55% or less. By setting the crystallinity of the powdery liquid crystalline resin to 10% or more and 60% or less, the orientation of the resin during hot press molding can be further reduced, and a hot press molded article having a smaller anisotropy can be produced. In addition, the strength of the hot press molded product can be improved, and the heat resistance can be further improved. The crystallinity can be measured by an X-ray diffraction apparatus. When the crystallinity does not satisfy the above range, the crystallinity can be adjusted to the above range by heat-treating the liquid crystalline resin. For example, the crystallinity of the liquid crystalline resin can be adjusted to the above range by heat-treating the resin at a temperature ranging from the glass transition temperature Tg to the melting point Tm 2. The measurement of the glass transition temperature Tg can be performed by dynamic viscoelasticity measurement.
The melting point Tm2 of the powdery liquid crystalline resin measured by a differential scanning calorimeter is 250 ℃ or more and 400 ℃ or less, preferably 260 ℃ or more and 380 ℃ or less, more preferably 280 ℃ or more and 350 ℃ or less. By setting the melting point Tm2 to 250 ℃ or higher and 400 ℃ or lower, the orientation of the resin during hot press molding can be further reduced, and a hot press molded article having less anisotropy can be produced. In addition, the strength of the hot press molded product can be improved, and the heat resistance can be further improved.
The melting point Tm2 is set to the following temperature: the temperature of the peak top of the endothermic peak observed when heating was carried out at a temperature rising rate of 20 ℃/min from room temperature (1stRUN) (melting point Tm1) was measured by a method based on JIS K-7121(1999), and then, the temperature was maintained at (melting point Tm1+40) ° c for 2 minutes, followed by cooling to room temperature at a temperature lowering rate of 20 ℃/min, and the temperature of the peak top of the endothermic peak of 2ndRUN observed when heating was carried out again at a temperature rising rate of 20 ℃/min from room temperature (2 ndRUN). The temperature at which melting point Tm1 (the temperature at which the peak starts to rise) described later starts in the endothermic peak of 1 stun described above.
The difference Δ Tm (Tm2-Tm1 onset temperature) between the melting point Tm2 and the melting point Tm1 of the powdery liquid crystalline resin measured by a differential scanning calorimeter is preferably 30 ℃ or higher and 90 ℃ or lower, more preferably 40 ℃ or higher and 80 ℃ or lower. When the difference Δ Tm between the starting temperatures of melting point Tm2 and melting point Tm1 is in this range, the processability during hot press molding can be improved and the heat resistance of the hot press molded article can be improved.
A barrel temperature and a shear rate of the powdery liquid crystalline resin at 10to 30 ℃ higher than a melting point Tm2 measured by a differential scanning calorimeter, and 100sec-1The melt viscosity measured below is preferably 10 pas or more and 1000 pas or less, more preferably 50 pas or more and 800 pas or less. The melt viscosity measured at a barrel temperature 10to 30 ℃ higher than the melting point Tm2 is a melt viscosity measured at any temperature suitably selected depending on the kind of the liquid crystalline resin at a barrel temperature 10to 30 ℃ higher than the melting point Tm2, and the melt viscosity measured at all temperatures 10to 30 ℃ higher than the melting point Tm2 is not necessarily within the above range. By setting the melt viscosity of the powdery liquid crystalline resin in the above range, the appearance of the hot press molded article can be improved. The melt viscosity can be adjusted by adjusting the final polymerization temperature at the time of melt polymerization of the liquid crystalline resin. For example, the melt viscosity can be adjusted to 10 pas by the final polymerization temperature at the time of melt polymerization of the liquid crystalline resin at a temperature exceeding 300 ℃.
The shape of the fine particles in the powdery liquid crystalline resin is not particularly limited, and may be any form such as spherical (including substantially spherical), spindle-shaped, amorphous granular, fibril-shaped, and fibrous, and spherical (including substantially spherical) and amorphous granular are preferable in terms of powder flowability.
[ Hot Press Molding ]
The hot press molded article is a molded article formed of the powdery liquid crystalline resin. By using the powdery liquid crystalline resin, a hot press molded article having a small anisotropy can be formed. Since the anisotropy is small, physical properties such as strength and heat resistance can be made uniform in the resin flow direction and the direction perpendicular thereto, and a highly reliable molded article can be formed. Thus, the resin composition can be preferably used as an automobile part used at high temperature, an electric/electronic part mounted in a solder reflow step, a flexible copper-clad laminate, or the like. The hot press molded article may be configured as a film-shaped molded article having a thickness of less than 2mm, for example.
The production of the hot press molded article can be carried out as follows: the powder material containing the powdery liquid crystalline resin is obtained by pressure molding at a temperature (for example, 250 to 400 ℃) not lower than the melting point Tm2 of the powdery liquid crystalline resin using a hot press molding machine. The pressure at the time of molding is not particularly limited, and may be a pressure capable of molding to a desired thickness.
The powder material may contain 1 or more of the powdery liquid crystalline resins. The total content of the powdery liquid crystalline resin is preferably 50 mass% or more, and more preferably 70 mass% or more in the powder material for hot press molding. The upper limit value is not particularly limited, and may be, for example, 95 mass% or less.
The powder material may contain additives such as inorganic fillers in addition to the powdery liquid crystalline resin, depending on the physical properties and applications required for the molded article to be obtained. Examples of the inorganic filler include a particulate filler having an average particle diameter of 500nm or less or 400nm or less, a plate-like filler, and a fibrous filler having an average fiber length of 100 μm or less. The material of the inorganic filler is not particularly limited, and for example, the same inorganic filler as that which can be blended with the liquid crystal resin can be used. By using the powder-particle filler and the plate-like filler having the above average particle diameter, the powder flowability and dispersibility of the liquid crystalline resin fine particles can be improved. By using the fibrous filler having the above average particle diameter, the strength of the obtained hot press molded article can be further improved. The average particle diameter can be measured by the same method as that for the resin fine particles. The average fiber length can be measured, for example, using a Nicole co., ltd. The content of the inorganic filler is preferably 50% by mass or less, more preferably 30% by mass or less in the powder material.
The mixing method for forming the mixture with the powdery liquid crystalline resin may be a conventionally known method, and for example, a mixing method using shaking, a mixing method involving pulverization using a ball mill or the like, a mixing method using a stirring blade such as a henschel mixer, or the like may be used. As other additives, antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, and the like can also be used.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
The liquid crystalline resins LCP 1-4 used in the examples and comparative examples were produced as follows.
Production example 1 LCP 1: wholly aromatic polyester
After the following raw materials were charged into a polymerization vessel, the temperature of the reaction system was raised to 140 ℃ and the reaction was carried out at 140 ℃ for 1 hour. Then, the temperature was raised to 325 ℃ over a further 3.5 hours, and from this temperature, the pressure was reduced to 5Torr (i.e., 667Pa) over a further 20 minutes, and polycondensation was carried out while distilling off acetic acid, excess acetic anhydride and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen gas was introduced, the pressure was increased from a reduced pressure state to a normal pressure state, and the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain LCP1 pellets.
(raw materials)
4-hydroxybenzoic acid (HBA); 1660g (73 mol%)
6-hydroxy-2-naphthoic acid (HNA); 837g (27 mol%)
Metal catalysts (potassium acetate catalysts); 165mg
An acylating agent (acetic anhydride); 1714g
Production example 2 LCP 2: wholly aromatic polyester
After the following raw materials were charged into a polymerization vessel, the temperature of the reaction system was raised to 140 ℃ and the reaction was carried out at 140 ℃ for 1 hour. Thereafter, the temperature was further raised to 330 ℃ over 3.5 hours, and from this temperature, the pressure was reduced to 10Torr (i.e., 1330Pa) over 15 minutes, and polycondensation was carried out while distilling off acetic acid, excess acetic anhydride and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen gas was introduced, the pressure was increased from a reduced pressure state to a normal pressure state, and the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain LCP2 pellets.
(raw materials)
4-hydroxybenzoic acid (HBA); 2524g (79.3 mol%)
6-hydroxy-2-naphthoic acid (HNA); 867g (20 mol%)
Terephthalic Acid (TA); 27g (0.3 mol%)
Metal catalysts (potassium acetate catalysts); 150mg of
An acylating agent (acetic anhydride); 2336g
Production example 3 LCP 3: wholly aromatic polyester amide
After the following raw materials were charged into a polymerization vessel, the temperature of the reaction system was raised to 140 ℃ and the reaction was carried out at 140 ℃ for 1 hour. Thereafter, the temperature was further raised to 340 ℃ over 4.5 hours, and from this temperature, the pressure was reduced to 10Torr (i.e., 1330Pa) over 15 minutes, and polycondensation was carried out while distilling off acetic acid, excess acetic anhydride and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen gas was introduced, the pressure was increased from a reduced pressure state to a normal pressure state, and the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain LCP3 pellets.
(raw materials)
4-hydroxybenzoic acid (HBA); 1380g (60 mol%)
6-hydroxy-2-naphthoic acid (HNA); 157g (5 mol%)
Terephthalic Acid (TA); 484g (17.5 mol%)
4, 4' -dihydroxybiphenyl (BP); 388g (12.5 mol%)
4-acetoxyaminophenol (APAP); 160g (5 mol%)
Metal catalysts (potassium acetate catalysts); 110mg
An acylating agent (acetic anhydride); 1659g
Production example 4 LCP 4: wholly aromatic polyester
After the following raw materials were charged into a polymerization vessel, the temperature of the reaction system was raised to 140 ℃ and the reaction was carried out at 140 ℃ for 1 hour. Thereafter, the temperature was raised to 360 ℃ over a further 5.5 hours, and from this temperature, the pressure was reduced to 5Torr (i.e., 667Pa) over a further 30 minutes, and melt polymerization was carried out while distilling off acetic acid, excess acetic anhydride and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen gas was introduced, the pressure was increased from a reduced pressure state to a normal pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strand was pelletized to obtain pellets. The obtained pellets were heated from room temperature to 290 ℃ over 20 minutes under a nitrogen atmosphere, and after holding for 3 hours, they were naturally cooled to obtain LCP4 pellets.
(raw materials)
4-hydroxybenzoic acid (HBA); 37g (2 mol%)
6-hydroxy-2-naphthoic acid (HNA); 1218g (48 mol%)
Terephthalic Acid (TA); 560g (25 mol%)
4, 4' -dihydroxybiphenyl (BP); 628g (25 mol%)
Metal catalysts (potassium acetate catalysts); 165mg
An acylating agent (acetic anhydride); 1432g
(deflection temperature under load)
The pellets of the production example were molded by a molding machine (SE 100DU, manufactured by Sumitomo heavy mechanical industries Co., Ltd.) under the following molding conditions to prepare test pieces of 80 mm. times.10 mm. times.3.2 mm. Using the test piece, the deflection temperature under load was measured in accordance with ASTM D648. The bending stress used was 1.8 MPa. The results are shown in Table 1.
[ Forming Condition ]
Barrel temperature:
300℃(LCP1)
340℃(LCP2)
350℃(LCP3)
370℃(LCP4)
temperature of the die: 80 deg.C
Injection speed: 33 mm/sec
[ example 1]
LCP1 was subjected to wet pulverization treatment using Mascoroider (MKZA 10-15JP, manufactured by Zengh industries, Ltd.) at a temperature of 35 ℃ and then spray-dried to obtain a powdery liquid crystalline resin. The melt viscosity, average particle diameter, maximum particle diameter, crystallinity, and melting point (Tm2, Tm1 onset temperature) of the powdery liquid crystalline resin were measured by the following methods.
Using the obtained powdery liquid crystalline resin, a film having a radius of 50mm and a thickness of 0.1mm was produced by a hot Press molding machine ("Mini Test Press-10" manufactured by Toyo Seiki Seisaku-Sho Ltd.) under a pressure of 290 ℃ and a pressure of 3 MPa. The orientation of the resin was evaluated for the obtained film by the following method.
[ example 2]
Press-molded films were obtained in the same manner as in example 1 except that the liquid crystalline resin was used as shown in table 1 and the pressing temperature was 330 ℃. The powdery liquid crystalline resin and the film thus obtained were subjected to various physical properties measurement in the same manner as in example 1, and the orientation of the resin was evaluated.
Comparative example 1
Press-molded films were obtained in the same manner as in example 1 except that the liquid crystalline resin was used as shown in table 1 and the pressing temperature was 340 ℃. The powdery liquid crystalline resin and the film thus obtained were subjected to various physical properties measurement in the same manner as in example 1, and the orientation of the resin was evaluated.
Comparative example 2
A hot press molded film was obtained in the same manner as in example 2, except that the pellets of LCP2 were used as they were. The powdery liquid crystalline resin and the film thus obtained were subjected to various physical properties measurement in the same manner as in example 1, and the orientation of the resin was evaluated.
Comparative example 3
A hot press molded film was obtained in the same manner as in example 1 except that the liquid crystalline resin was changed to a pressure temperature of 360 ℃. The powdery liquid crystalline resin and the film thus obtained were subjected to various physical properties measurement in the same manner as in example 1, and the orientation of the resin was evaluated.
[ measurement and evaluation ]
The method for measuring the melt viscosity, average particle diameter, maximum particle diameter, crystallinity, and melting point (Tm2, Tm1 onset temperature) of the powdery liquid crystalline resin, and the method for evaluating the orientation of the resin are as follows. The results are shown in Table 1.
(melt viscosity)
The apparent melt viscosity was measured by a capillary rheometer (Capillograph 1D: piston diameter 10mm, manufactured by Toyo Seiki Seisaku-Sho Ltd.) under the following conditions in accordance with ISO 11443. An orifice having an inner diameter of 1mm and a length of 20mm was used for the measurement.
Barrel temperature:
300℃(LCP1)
340℃(LCP2)
350℃(LCP3)
370℃(LCP4)
shearing speed: 100sec-1
(average particle diameter and maximum particle diameter)
The average particle diameter and the maximum particle diameter were measured by using a laser diffraction/scattering particle size distribution measuring apparatus (LA-920, manufactured by horiba, Ltd.) and methanol as a dispersion solvent. The average particle size is an arithmetic average particle size on a volume basis.
(degree of crystallinity)
From the diffraction information (wide-angle X-ray diffraction pattern or wide-angle X-ray curve) obtained by the X-ray diffractometer (D2 PHASER, Bruker corporation), the amorphous-derived scattering region and the crystal-derived scattering region were separated, and the crystallinity was measured according to the following formula (I) by the method described in w.ruland, Acta cryst., 14, 1180 (1961).
Degree of crystallinity (%) [ scattering intensity derived from crystal/(scattering intensity derived from crystal + scattering intensity derived from amorphous) ] × 100 · (I)
(melting Point Tm2 and melting Point Tm1 Start temperature)
The temperature of the peak top of the endothermic peak observed when heating was carried out at a temperature rise rate of 20 ℃/min from room temperature (1 sturn) (melting point Tm1) was measured by a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Corporation, DSC7000X), and then, the temperature was maintained at a temperature of (melting point Tm1+40) ° c for 2 minutes, followed by cooling to room temperature at a temperature fall rate of 20 ℃/min, and the temperature of the peak top of the endothermic peak of 2ndRUN observed when heating was carried out again at a temperature rise rate of 20 ℃/min from room temperature was measured as melting point Tm 2. The temperature at the beginning of the endothermic peak of 1 sturn (temperature at which the peak starts to rise) was measured as the melting point Tm1 onset temperature.
(evaluation of orientation of resin)
A surface photograph of the film was taken with an optical microscope (ultra-deep double-angle microscope, product of KEYENCE, Inc. "VHX-D510"). The obtained photographs are shown in fig. 1 and 2. The surface was observed and evaluated according to the following criteria.
Good: no stripe pattern is present.
Poor: there is a striped pattern.
[ Table 1]
Claims (9)
1. A powdery liquid crystalline resin for hot press moldings, which contains 90 mol% or more of a structural unit derived from an aromatic hydroxycarboxylic acid in all the structural units, and which has an average particle diameter of 10to 300 [ mu ] m.
2. The powdery liquid crystalline resin according to claim 1, wherein the crystallinity is 10% or more and 60% or less.
3. The powdery liquid crystalline resin according to claim 1 or 2, wherein a difference Δ Tm (Tm2-Tm1 onset temperature) between the onset temperatures of a melting point Tm2 and a melting point Tm1 as measured by a differential scanning calorimeter is 30 ℃ or more and 90 ℃ or less.
4. The powdery liquid crystalline resin according to any one of claims 1 to 3, wherein a melting point Tm2 measured by a differential scanning calorimeter is 250 ℃ or more and 400 ℃ or less.
5. The powdery liquid crystalline resin according to any one of claims 1 to 4, wherein the shear rate is 100sec at a cylinder temperature 10to 30 ℃ higher than the melting point Tm2 measured by a differential scanning calorimeter-1The melt viscosity measured below is 10 pas or more and 1000 pas or less.
6. The powdery liquid crystalline resin according to any one of claims 1 to 5, wherein the ratio of the maximum particle diameter to the average particle diameter (maximum particle diameter/average particle diameter) is 5 or less.
7. A powder material for hot press molded articles, which comprises the powdery liquid crystalline resin according to any one of claims 1 to 6.
8. A hot press molded article comprising the powdery liquid crystalline resin according to any one of claims 1 to 6.
9. The hot press molded article according to claim 8, which is in the form of a film having a thickness of less than 2 mm.
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| JP2005178056A (en) * | 2003-12-17 | 2005-07-07 | Polyplastics Co | Molding method of liquid crystalline polyester resin |
| JP2011000791A (en) * | 2009-06-18 | 2011-01-06 | Nissei Plas-Tech Corp | Method for molding crystalline liquid crystal polymer, and molding thereof |
| WO2015016141A1 (en) * | 2013-07-31 | 2015-02-05 | 東レ株式会社 | Method for producing liquid crystalline polyester, and liquid crystalline polyester |
| CN105073375A (en) * | 2013-03-26 | 2015-11-18 | 日本轻金属株式会社 | Metal-resin bonded body, and production method therefor |
| JP2017095600A (en) * | 2015-11-25 | 2017-06-01 | 上野製薬株式会社 | Liquid crystal polymer |
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| JP2002275283A (en) * | 2001-03-21 | 2002-09-25 | Sekisui Chem Co Ltd | Film reinforced with liquid crystal resin fiber, laminated sheet and interior material for automobile |
| JP2003292638A (en) * | 2002-03-29 | 2003-10-15 | Kuraray Co Ltd | High heat-resistant film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005178056A (en) * | 2003-12-17 | 2005-07-07 | Polyplastics Co | Molding method of liquid crystalline polyester resin |
| JP2011000791A (en) * | 2009-06-18 | 2011-01-06 | Nissei Plas-Tech Corp | Method for molding crystalline liquid crystal polymer, and molding thereof |
| CN105073375A (en) * | 2013-03-26 | 2015-11-18 | 日本轻金属株式会社 | Metal-resin bonded body, and production method therefor |
| WO2015016141A1 (en) * | 2013-07-31 | 2015-02-05 | 東レ株式会社 | Method for producing liquid crystalline polyester, and liquid crystalline polyester |
| JP2017095600A (en) * | 2015-11-25 | 2017-06-01 | 上野製薬株式会社 | Liquid crystal polymer |
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